DaEun Yang

We synthesized various phosphonium- and ammonium-based ionic liquids (ILs), using benzenesulfonate (BS) and 4-methylbenzenesulfonate (MBS) to establish the criteria for designing an ideal draw solute in a forward osmosis (FO) system. Additionally, the effects of monocationic, dicationic, and anionic species on FO performance were studied. Monocationic compounds ([P₄₄₄₄][BS], [P₄₄₄₄][MBS], [N₄₄₄₄][BS], and [N₄₄₄₄][MBS]) were obtained in one step via anion exchange. Dicationic compounds ([(P₄₄₄₄)₂][BS], [(P₄₄₄₄)₂][MBS], [(N₄₄₄₄)₂][BS], and [(N₄₄₄₄)₂][MBS]) were prepared in two steps via a Menshutkin SN₂ reaction and anion exchange. We also investigated the suitability of ILs as draw solutes for FO systems. The aqueous [P₄₄₄₄][BS], [N₄₄₄₄][BS], [N₄₄₄₄][MBS], and [(N₄₄₄₄)₂][BS] solutions did not exhibit thermoresponsive behavior. However, 20 wt% [P₄₄₄₄][MBS], [(P₄₄₄₄)₂][BS], [(P₄₄₄₄)₂][MBS], and [(N₄₄₄₄)₂][MBS] had critical temperatures of approximately 43, 33, 22, and 60 °C, respectively, enabling their recovery using temperature. An increase in IL hydrophobicity and bulkiness reduces its miscibility with water, demonstrating that it can be used to tune its thermoresponsive properties. Moreover, the FO performance of 20 wt% aqueous [(P₄₄₄₄)₂][MBS] solution was tested for water flux and found to be approximately 10.58 LMH with the active layer facing the draw solution mode and 9.40 LMH with the active layer facing the feed solution.

A series of phosphonium-based ionic liquids (ILs) based on benzenesulfonate derivatives (tetrabutylphosphonium benzenesulfonate ([TBP][BS]), tetrabutylphosphonium 4-methylbenzenesulfonate ([TBP][MBS]), tetrabutylphosphonium 2,4-dimethylbenzenesulfonate ([TBP][DMBS]), and tetrabutylphosphonium 2,4,6-trimethylbenzenesulfonate ([TBP][TMBS])) were synthesized via anion exchange with tetrabutylphosphonium bromide ([TBP][Br]). Then, we characterized the ILs and investigated their suitability as draw solutes for forward osmosis (FO), focusing on their thermoresponsive properties, conductivities, and osmotic pressures. We found that aqueous [TBP][BS] was not thermoresponsive, but 20 wt% aqueous [TBP][MBS], [TBP][DMBS], and [TBP][TMBS] had lower critical solution temperatures (LCSTs) of approximately 41, 25, and 21 °C, respectively, enabling their easy recovery using waste heat. Based on these findings, 20 wt% aqueous [TBP][DMBS] was tested for its FO performance, and the water and reverse solute fluxes were found to be approximately 9.29 LMH and 1.37 gMH, respectively, in the active layer facing the draw solution (AL-DS) mode and 4.64 LMH and 0.37 gMH, respectively, in the active layer facing the feed solution (AL-FS) mode. Thus, these tetrabutylphosphonium benzenesulfonate-based LCST-type ILs are suitable for drawing solutes for FO process.

We synthesized sustainable 2,4-di-tert-butylphenoxymethyl-substituted polystyrenes (PDtBP#, # = 88, 68, 35, and 19, where # is molar percent contents of 2,4-di-tert-butylphenoxymethyl moiety), using post-polymerization modification reactions in order to study their liquid crystal (LC) alignment behaviors. In general, LC cells fabricated using polymer film with higher molar content of 2,4-di-tert-butylphenoxymethyl side groups showed vertical LC alignment behavior. LC alignment behavior in LC cell was related to the surface energy of the polymer alignment layer. For example, when the total surface energy value of the polymer layer was smaller than about 29.4 mJ/m², vertical alignment behaviors were observed, generated by the nonpolar 2,4-di-tert-butylphenoxymethyl moiety with long and bulky carbon groups. Orientation stability was observed at 200 °C in the LC cells fabricated using PDtBP88 as the LC alignment layer. Therefore, as a natural compound modified polymer, PDtBP# can be used as a candidate LC alignment layer for environmentally friendly applications.

We synthesized a series of polystyrene derivatives containing various side groups, such as the 4-(tert-butyl)-phenoxymethyl, 3-(tert-butyl)-phenoxymethyl, 2-(tert-butyl)-phenoxymethyl, 4-cumyl-phenoxymethyl, and 4-trityl-phenoxymethyl groups, through a polymer modification reaction to examine the liquid crystal (LC) alignment of these derivatives. In general, the vertical LC alignment on polymer films can be affected by the position and structure of the terminal moiety of the polymer side group. For example, the LC cells fabricated with 4-(tert-butyl)-phenoxymethyl-substituted polystyrene having a tert-butyl moiety as a para-type attachment to the phenoxy groups of the polystyrene derivatives exhibited vertical LC alignment, whereas the LC cells prepared from 3-(tert-butyl)- and 2-(tert-butyl)-phenoxymethyl-substituted polystyrene films exhibited planar LC alignment. In addition, the LC cells fabricated from 4-cumyl- and 4-trityl-phenoxymethyl-substituted polystyrene films with additional phenyl rings in the side groups exhibited planar LC alignment, in contrast to the LC alignment of the (tert-butyl)-phenoxymethyl-substituted polystyrene series. The vertical LC orientation was well correlated with the surface energy of these polymer films. For example, vertical LC orientation, which mainly originates due to the nonpolar tertiary carbon moiety having bulky groups, was observed when the surface energy of the polymer was lower than 36.6 mJ/m².

We synthesized a series of renewable and plant-based isoeugenol-substituted polystyrenes (PIEU#, # = 100, 80, 60, 40, and 20, where # is the molar percent content of isoeugenol moiety), using polymer modification reactions to study their liquid crystal (LC) alignment behavior. In general, the LC cells fabricated using polymer film with a higher molar content of isoeugenol side groups showed vertical LC alignment behavior. This alignment behavior was well related to the surface energy value of the polymer layer. For example, vertical alignments were observed when the polar surface energy value of the polymer was smaller than approximately 3.59 mJ/m², generated by the nonpolar isoeugenol moiety with long and bulky carbon groups. Good alignment stability at 100 °C and under ultraviolet (UV) irradiation of 15 J/cm² was observed for the LC cells fabricated using PIEU100 as a LC alignment layer. Therefore, renewable isoeugenol-based materials can be used to produce an eco-friendly vertical LC alignment system.